Control of undesirable vegetation



United States Patent 3,235,358 CfiNTRGL 0F UNDESIRABLE VEGETATIUN Edward J. Soboczenski, Chadds Ford, Pa., assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware N0 Drawing. Filed Sept. 6, 1962, Ser. No. 221,890 11 Claims. (Cl. 71-25) This application is a continuation-in-part ofcopending applications Serial No. 89,673, filed February 16, 1961; and Serial No. 12,956, filed March 7, 1960, both now abandoned.

This invention relates to the use of 3,5-substituted uracils as herbicides, and is more particularly directed to herbicidal compositions and methods employing, as an active ingredient, at least one compound of the formula R-N R-N J H e l X HX- Where:

R is

Alkyl of 1 through carbon atoms,

Substituted alkyl of 1 through 10 carbon atoms,

Aryl of 5 through 14 carbon atoms,

Substituted aryl of 5 through 14 carbon atoms,

Arakyl of 5 through carbon atoms,

Substituted aralkyl of 5 through 15' carbon atoms,

Alkenyl of 3 through 10 carbon atoms,

Alkynyl of 3 through 10 carbon atoms,

Cycloalkyl of 3 through 12 carbon atoms,

Cycloalkenyl of 4 through 12 carbon atoms,

Cycloalkyl alkyl of 4 through 13 carbon atoms,

Cycloalkenyl alkyl of 5 through 13 carbon atoms,

(Substituted cycloalkyl)alkyl of 5 through 14 carbon atoms,

(Substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms,

Or cyano;

R is chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro, alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of 1 through 6 carbon atoms, alkenyl of 3 through 6 carbon atoms, thiocyano, cyano, methylthiol, alkylthio of 1 through 4 carbon atoms, methylthiomethyl, chloromethyl, bromomethyl, fluoromethyl, phenylthiomethyl, or carboxymethylthiomethyl,

with the proviso that R can be hydrogen when R is cycloalkyl, cycloalkenyl, cycloalkyl alkyl, or cycloalkenyl alkyl;

and

X is oxygen or sulfur.

The salts of these compouds can also be used according to this invention. By salts is meant those compounds formed with such cations as sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese and quaternary ammonium.

Some of the uracils of Formula 1 also form novel 1:1 addition compounds with nitrogenous bases. The exact structure of these compounds is not known. Although the compounds are, generally speaking, poorly soluble in water, they are, according to the best available information, believed to be essentially salt-like in structure. They will be symbolized by the following formula, with the 3,235,358 Patented Feb. 15, 1966 understanding that it is representative only, and is not intended to illustrate actual structure:

R RN I 1 NB o H where:

R and R are defined as in Formula 1,

and

The amines can be primary, secondary or tertiary amines, polyamines, arylamines, or heterocyclicamines. Illustrative of such amines are:

Sec.-butylamine 2-amino-2-methyl-1,3-propanediol Trimethylenediamine Ethanolamine Dodecylamine Ethylenediamine Hexamethylenediamine Cocoadiamine Tallowdiamine Hexamethyleneimine Cyclohexylamine Methoxypropylamine Methylamine Dimethylamine Trimethylamine Ammonia Ethylamine Propylamine Butylamine Octylamine Pyridine Piperidine Tetramethylguanidine Acetamidine Benzylamine Diethylenediamine Z-aminobutanol-l 2-aminooctanol-1 Within the scope of Formula 1 is a group of novel compounds. These are of the formula 3 O U H where R is phenyl, substituted phenyl, cycloalkyl, of 3 through 12 carbon atoms, cycloalkenyl of 5 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon atoms, substituted cycloalkyl alkyl of 5 through 14 carbon atoms, or

wherein:

X is methyl or ethyl, Y is hydrogen or methyl, and Z is an alkyl group of less than 6 carbon atoms;

and R is halogen, methyl, hydroxymethyl, methoxymethyl, or

nitro; and the salts of these compounds as defined in Formulae 1 and 2.

The substituted uracils of Formula 1 also form Water stable, novel complexes with phenol and substituted phenols. These complexes have the formula (4) H O X I II I T F HO\\N/ n in-1 where:

R and R are as defined in Formula 1,

X is hydrogen, chlorine, nitro, alkyl of 1 through 3 carbon atoms, bromine or R R is alkyl of 1 through 3 carbon atoms,

Y is chlorine or alkyl of 1 through 3 carbon atoms,

In is a number 1 through 5, and

n is 1 or 2.

These complexes are also herbicidal, and in this respect, have some advantages over the uracils per se, viz., higher solubility in oils and solvents. They are formulated into herbicidal compositions in the same way as are the uracils themselves.

In Formulae 1 to 4 and Formula 5, which follows, the term substituted alkyl is intended to include such radicals as Bromoalkyl of 1 through carbon atoms,

Chloroalkyl of 1 through 10 carbon atoms, Hydroxyalkyl of 1 through 10 carbon atoms, Alkoxyalkyl of 2 through 10 carbon atoms,

Alkoxy carbonyl alkyl of 3 through 10 carbon atoms, Dialkyl amino alkyl of 3 through 10 carbon atoms, and Cyonoalkyl of 2 through 10 carbon atoms.

Similarly, the terms aryl and substituted aryl embrace radicals such as Phenyl,

Naphthyl,

o-Biphenylyl,

Pyridyl,

Chlorophenyl,

Methoxyphenyl,

Bromophenyl,

Dichlorophenyl,

Dibromophenyl,

Fluorophenyl,

Trichlorophenyl,

Alkylphenyl of 7 through 11 carbon atoms, Dialkylphenyl of 8 through 12 carbon atoms, Choloroalkylphenyl 7 through 10 carbon atoms, Nitrochlorophenyl,

Nitrophenyl,

Dichloronitrophenyl,

Chloroalkoxyphenyl of 7 through 11 carbon atoms, Trifluoromethylphenyl,

Alkylnaphthyl of 11 through 15 carbon atoms, Chloronaphthyl,

Tetrahydronaphthyl, and

Indenyl.

The terms aralkyl and substituted aralkyl are intended to include such radicals as Furfuryl, Benzyl, Phenylalkyl of 8 through 11 carbon atoms (total),

i Chlorobenzyl, Dichlorobenzyl, Alkylbenzyl of 8 through 11 carbon atoms (total), Dialkylbenzyl of 9 through 13 carbon atoms (total), Nitrobenzyl, Alkoxybenzyl of 8 through 11 carbon atoms (total), and Naphthylmethyl.

The terms cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will include Cyclohexyl,

Cyclohexenyl,

Cyclohexylalkyl,

Cyclohexenyl alkyl,

Cyclooctyl,

Cyclododecyl,

Cyclopentyl,

Cyclopentenyl,

Cyclopentyl alkyl,

Cyclopentenyl alkyl,

Norbornyl,

Norbornenyl,

Norbornyl alkyl,

Norbornenyl alkyl,

Bicyclo (2,2,2) octyl,

Bicyclo (2,2,2) octenyl,

Bicyclo (2,2,2) octyl alkyl,

Bicyclo (2,2,2) octenyl alkyl, Cyclopropyl,

Cyclobutyl,

Cyclobutyl alkyl,

Cyclobutenyl,

Cyclobutenyl alkyl, Hexahydroindanyl, Tetrahydroindanyl, Hexahydroindenyl,

Hexahydroindenyl alkyl, Tetrahydroindanyl alkyl, Hexahydroindanyl alkyl, Hexahydro-4,7-methanoindenyl, Tetrahydro-4,7-methanoindanyl, Hexahydro-4,7-methanoindanyl, Hexahydro-4,7-methanoindenyl alkyl, Tetrahydro-4,7-methanoindanyl alkyl, Hexahydro-4,7-methanoindanyl alkyl, Decahydronaphthyl, Decahydronapht'hyl alkyl, Tetrahydronaphthyl, Tetrahydronaphthyl alkyl, Decahydro-1,4-methanonaphthyl, Decahydro-1,4-methanonaphthyl alkyl, Octahydro-1,4-methanonaphthyl, Octahydro-1,4-methanonaphthyl alkyl, Decahydro-1,4-5,S-dimethanonaphthyl, Deca'hydro-1,4-5,8-dimethanonaphthyl alkyl, Octahydro-1,4-5,S-dimethanonaphthyl, Octahydro- 1 ,4-5 ,8-dimethanonaphthyl alkyl.

These cyclic substituents can be further substituted with alkyl groups of 1 through 4 carbon atoms, methoxy, chlorine and bromine.

UTILITY These compounds broad spectrum herbicidal activity makes them useful wherever general weed control is required, such as on industrial sites, on railroad ballast and in noncrop agricultural areas. For example, a pre-emergence treatment with these compounds will control such germinating broadleaf weeds as pigweed, lambs quarter, mustard, chickweed and ragweed, and such grass weeds as crab grass and foxtails.

The uracils can also be used in soil foliage applications for the control of such broadleaves as pigweed, lambs quarter, mustard, chickweed and ragweed and such grass weeds as crab grass, foxtails, quack grass and seedling Johnson grass.

Certain of the uracils exhibit selective herbicidal action in crops. For example, by properly selecting a uracil of the invention and a rate and time of application, annual Weeds growing in fields of peanuts can be controlled. This selective activity is described in greater detail in the examples which follow.

The concentration at which the compounds are to be used Will vary according to the result desired, the type of vegetation, the formulation used, the mode of application, weather conditions, foliage density, and other similar factors. Since so many factors play a role it is not possible to indicate a concentration suitable for all situations. Generally, when they are used in pre-emergence treatments, the uracils are used at concentrations of from 0.25 to pounds of active ingredient per acre. Concentrations of from 0.5 to 4 pounds per acre are preferred. When used in soil-foliage applications, the uracils are used at concentrations of from to 35 pounds of active ingredient per acre. The optimum concentration to be used in any particular application will be readily apparent to one skilled in the art.

Preferred for use according to this invention because of their greater effectiveness at lower rates of application are compounds of the formula R N |-Ri where:

R is

Alkyl of 2 through 8 carbon atoms, Substituted alkyl of 2 through 8 carbon atoms, P-henyl, substituted phenyl, Aralkyl of 5 through 10 carbon atoms, Substituted aralkyl of 5 through 10 carbon atoms, Cycloalkyl of from 3 through 12 carbon atoms, Substituted cycloalkyl of from 4 through 12 carbon atoms, Cycloalkenyl of 5 through 12 carbon atoms, Substituted cycloalkenyl of 5 through 12 carbon atoms, Cycloalkyl alkyl of 4 through 13 carbon atoms, (Substituted cycloalkyl)alkyl of 4 through 13 carbon atoms, and

R is chlorine, bromine, iodine, methyl, hydroxymethyl,

methoxymethyl, or nitro.

PREPARATION OF COMPOUNDS The substituted uracils used according to this invention can be prepared according to the following equations:

The cyclohexylurea of Equation 6 is condensedwith the tat-methyl oxalacetate in an inert solvent such as benzene, and in the presene of an acidic catalyst such as phosphoric acid. This reaction mixture is heated until approximately the theoretical amount of Water has been removed. This will vary according to the starting materials used. The solvent is then removed and the residue is heated at reflux With a slight excess of aqueous sodium hydroxide, whereupon ring closure takes place. The resulting uracil carboxylic acid is decarboxylated to the desired uracial by heating it above its melting point, either by itself or in an inert, high-boiling-point liquid such as d-ibutyl phthalate or a eutectic mixture of diphenyl and diphenyl ether.

Other uracils can be prepared by substituting an appropriate substituted urea or thiourea for the cyclohexylurea in Equation 6.

-By substituting ethyl oxalacetate, u-cyano, a-fiuoro, aalkoxy, a-alkenyl, a-alkylthio, or a-alkyl oxalacetate for the a-methyl oxalacetate in Equation 6, the corresponding S-unsubstituted, 5-cyano, S-fluoro, S-alkoxy, 5-alkenyl, S-alkylthio and S-alkyl uracils can be prepared.

Uracils substituted in the 3-position can be prepared according to the equations which follow. These 3-substituted uracils can then be converted to 3,5-di-substituted uracils for use according to this invention.

and triethyl orthoforrnate, in molar ratios of 1:1:3, is heated at 70 C. to C. With stirring for 1 to 3 hours. The excess ortho ester and ethanol are then removed at reduced pressure. The residue consists of essentially pure (3-butylureido methylene] malononitrile.

This is dissolved in alcohol and converted to 3-sec.-butyl-S-cyanocytosine by treatment with sodium methylate, as illustrated in Equation 10.

The 3-sec.-butyl-5-cyanocytosine is converted to the corresponding uracil according to Equation 11 by a 3- hour reflux with 3 N hydrochloric acid. The uracil crystallizes from the aqueous solution on cooling.

On refluxing the 3-sec.-butyl-5-cyanouracil with an excess of 25% sodium hydroxide solution, the nitrile is hydrolyzed according to Equation 12 with the formation of 3-sec.-butyl-5-uracil carboxylic acid.

The acid is easily decarboxylated by heating it at a temperature above its melting point. This is illustrated by Equation 13. The result 3-sec.-butyluracil is purified by recrystallization from solvents such as nitromethane or carbon tetrachloride.

3,5-di-substituted uracils can also be prepared from the 3-substituted uracils made according to Equations 9 to 13 by reacting them with electrophilic reactants according to the following equation:

where A is bromine, chlorine, iodine, CH OH, fiSCN,

CHgCl, OI'

Other methods for preparing the uracils used according to this invention are set forth in J. Chem. Soc., 1956, 1877 and in J. Am. Chem. Soc., 74, 4267 (1952),

The salts of the compounds of Formula 1 are prepared by conventional methods such as dissolving the free uracil in an aqueous or nonaqueous solution of at least an equimolar amount of a base or basic salt containing the desired cation. For example, a sodium salt can be prepared by dissolving the uracil in water containing an equimolar amount of sodium hydroxide. The salt can then be isolated from the solution by removal of the water. The uracil salts which are not soluble in water can be prepared by treating an aqueous solution of an alkali metal salt of the uracil with an aqueous solution of a water-soluble salt of the metal.

The quaternary ammonium salts of the compounds of Formula 1 are prepared by reacting the substituted uracil with an appropriate quaternary ammonium hydroxide. solution, the reaction is most conveniently carried out in the same solvent. If the salt is desired, it can be easily prepared by removing the solvent.

Alternatively, the quaternary ammonium salts of the uracils can be prepared in a dry inert solvent such as toluene, methanol or xylene by first preparing the corresponding sodium salt in the solvent. The appropriate quaternary ammonium halide is then added with stirring and, if necessary, mild heating. The sodium halide which forms is removed by filtration, leaving the quaternary ammonium salt of the uracil in solution. If desired, the dry salt can be prepared by removing the solvent, preferably in vacuo.

The nitrogenous base-addition compound-s of Formula 2 are prepared by mixing together equimolar quantities of an appropriate uracil and a nitrogenous base. The mixture is gradually heated, with stirring, until a clear melt is formed. On cooling, the addition compound crystallizes. This product can then be recrystallized from a solvent such as benzene, cyclohexane, nitromethane or acetonitrile.

It is sometimes advantageous to use an inert solvent medium to carry out the reaction. Such a solvent moderates the reaction by acting as a heat sink, and allows better control of the reaction, especially if it is being car- Since these hydroxides are generally available in ried out on a large scale. Suitable inert solvents are benzene, cyclohexane, nitromethane, acetonitrile and dioxane.

When an inert solvent is used, the addition compounds are prepared by dissolving the amine in the solvent and then adding the uracil gradually, with stirring. Stirring is continued for from ten minutes to two hours. Mild heating may be necessary. Some addition compounds precipitate and can be removed by filtration. Other addition compounds are purified by evaporating the solvent. The addition compounds prepared in this way are suitable for use without further purification. However, they can be recrystallized as described above.

In some instances the uracil and amine are highly soluble in the inert solvent, but the addition compound is not, and so it can be filtered off pure when the reaction is complete.

The complexes of Formula 4 are formed by comelting the uracil and phenol in a 1:1 to 2:1 (uracilzphenol) ratio. They can also be formed by codissolving the reactants, in the same ratio, in a nonpolar solvent such as nitromethane or a mixture of nitromethane and cyclohexane. If the solvent-free complex is desired, it can be isolated by evaporating the solvent, preferably in vacuo. The complexes prepared in this way are suitable for formulation and herbicidal use without further purification.

HERBICIDAL COMPOSITIONS The uracil compounds described in Formulae 1 through 4 can be prepared for use by incorporating them with adjuvants.

The amount of herbicide in such preparations can vary over a wide range according to need. Generally speaking, they will contain from about 0.5 to by weight of a uracil.

Powder and dust preparations can be made by mixing uracils of the invention with finely-divided solids such as tales, natural clays, pyrophillite, diatomaceous earth; fiours such as walnut shell, wheat, redwood, soya bean and cotton seed; or inorganic substances such as magnesium carbonate, calcium carbonate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredient and the solid. The particles in such preparations are preferably less than 50 microns in average diameter.

Water-soluble preparations can be prepared by mixing a uracil with an alkaline solubilizing agent. Solid bases having a pH of at least 9.5 in a 1% aqueous solution such as sodium or potassium phosphates, silicates, carbonates, borates, oxides or hydroxides are suitable. The preparations can contain from 0.5 to 80% of active ingredient and from 5 to 99.5% of the solubilizing agent.

Granules and pellets can be made by mixing a finelydivided uracil with a suitable clay such as kaolinite, montmorillonite or attapulgite, moistening this mixture with from 15 to 20% by weight of water, and then extruding the mass through a suitable die under pressure. The extrusions are cut into predetermined lengths and then dried. These pellets can be granulated if desired.

Granules or pellets can also be prepared by spraying a suspension or solution of a uracil onto the surface of a preformed granule of clay, vermiculite or other suitable granular material. If the uracil is in solution, it will penetrate into the pores of the granule and so will adhere without the aid of a binding agent. When the active material is insoluble in the liquid and is carried as a suspension, it is preferable that a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added. In either case, the granule is then dried and ready for use.

The uracils can also be prepared in non-aqueous liquids. Aliphatic and aromatic hydrocarbons, especially those derived from petroleum and having boiling points of from C. to 400 C. are preferred. Hydrocarbons having lower boiling points should not be used because of their undesirable volatilization characteristics and inflammabil 9 ity. These liquid preparations are made by milling the components in a mill such as a pebble mill until the particles have average diameters of from 1 to 50 microns, preferably to 20 microns.

The herbicidal preparations, whatever physical form they take, can also contain a surface-active agent. The surfactant renders the preparations readily dispersible in liquids and improves their action on waxy leaves and the like. For general application, surface-active agents are used in the preparations at concentrations of from about 1 to by weight. Levels of from 0.5 to 6 parts of surfactant for each part of uracil, however, give unusual and unexpected results. Preparations having these higher levels of surfactants show greater herbicidal effectiveness than can be expected from a consideration of activity of the components used separately.

The term surface-active agent is intended to include wetting agents, dispersing agents, suspending agents and emulsifying agents. Surface-active agents suitable for use are set forth in Detergents and Emulsifiers Up-to- Date, 1962, John W. McCutcheon, Inc., Morristown, New Jersey. Other surface-active agents which can be used in these preparations are listed in U.S. Patents 2,139,- 276; 2,412,510; 2,426,417; 2,655,447; and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the U.S. Department of Agriculture.

The preparations can also optionally contain adhesives such as gelatin, blood albumin and such resins as rosin alkyd resins. These increase retention and tenacity of deposits following application.

The alkali metal salts of the compounds of Formula 1 are especially advantageous for use as herbicides because they are soluble in water and can be applied as aqueous solutions.

With respect to the nitrogenous base-addition compounds of Formula 2, it has been found that preparation with polar low-molecular weight amines such as ethanolamines, propanolamines and butanolamines gives addition compounds which are soluble in water, especially when the amine is present in excess. Other amines, such as piperidine and 'octanolamines give addition compounds which are soluble in both water (with an excess of amine present) and hydrocarbon solvents. At the other end of the scale, amines such as dodecylamines, cocoaarnines and tallowamines give the addition compounds high hydrocarbon solubility.

Thus, it is apparent that by properly selecting an amine and forming an addition compound with it, uracils of Formula 2 can be formulated as aqueous solutions, wettable powders, or as oil-emulsifiable or oil-extendable formulations. In this way, the nitrogenous base-addition compounds give formulation and application advantages, while still maintaining the desirable herbicidal characteristics of the parent uracils.

FORMULATIONS WITH OTHER HERBICIDES These herbicidal uracils can be combined with each other and with other known herbicides to give compositions which have advantages over the individual components.

Among the known herbicides which can be combined with the uracils are:

Substituted ureas 3 (3 ,4-dichlorophenyl)-1,1-dimethylurea 3 -'(4chlorop'henyl) -1,1-dimethylurea 3 -phenyl-1,1-dirnethylurea 1 3 -(3,4-dichlorophenyl)-3-methoxy1,1-dimethylurea 3-(4-chlorophenyl -3 -methoxy-1, l-dimethylurea 3-(3 ,4-dichlorophenyll-n-butyl-l-methylurea 3(3,4-dich1orophenyl) -1-methoxy-1-methylurea 3 (4-chlorophenyl l-methoxyl-methylurea 3 -'(3 ,4dichlorophenyl) -1,1,3-trimethylurea 3 3 ,4-dichlorophenyl)-1,1-diethylurea 3- (p-chlorophenoxyphenyl -1, l-dimethylurea 10 These ureas can be mixed with the uracels of this invention in proportions of from 1:4 to 4:1, respectively, the preferred ratio being 1:2 to 2:1.

Substituted triazines 2-chloro-4,6-bis (ethylamino) -s-triazine 2-chloro-4,6-bis isopropylarnino) -s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (methoxypropylamino) -s-triazine 2-methoxy-4,6-bis(isopropylamino) -s-triazine 2-ethylamino-4- Z-methoxyethylamino -6-chloro-striazine 2-methylmercapto-4,6-bis (isopropylamino -s-triazine 2-methylmercapto-4,6-bis (ethylamino -s-triazine 2-methylmercapto-4-ethylamino-6-isopropylamino-striazine Z-meth oxy-4,6-bis (ethylamino) -s-triazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-isopropylamino-4- Z-methoxyethylamino) -6-methylmercap-to-s-triazine These triazines can be mixed with the uracils of this invention in proportions 'of from 1:4 to 4: 1, respectively, the preferred ratio being 1:2 to 2: 1.

Phenols Dinitro-o-sec.-butylphenol and its salts Pentachlorophenol and its salts These phenols can be mixed with the uracils of this invention in the proportions of 1:10 to 10:1, respectively, the preferred ratio being 1:5 to 5: 1.

Carboxylic acids and derivatives The following carboxylic acids and derivatives can be mixed with the uracils of this invention in the listed respective proportions:

Mixed in a 1:20 to 8:1 ratio, preferably a 1:8 to 4:1 ratio.

2,6-dich1orobenzoni-trile Mixed in a 1:4 to 4:1 ratio, preferably a 1:3 to 3:1

ratio.

Trichloroacetic acid and its salts Mixed in a 1:4 to 25:1 ratio, preferably a 1:2 to 10:1 ratio.

2,2-dichloropropionic acid and its salts Mixed in a 1:4 to 10:1 ratio, preferably a 1:2 to 5:1 ratio.

N-phenylcarbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, isopropyl ester N-(m-chlorophenyl)carbamic acid, 4-chloro-2- butynyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:2 to 12:1 ratio.

2,3,6-trichloropl1enylacetic acid and its salts Mixed in a 1:20 to 8:1 ratio, preferably a 1:4 to 4:1

ratio.

2-chloro-N,N-diallylacetamide Maleic hydrazide Mixed in a 1:2 to :1 ratio, preferably a 1:1 to 5:1 ratio.

Inorganic and mixed inorganic-organic salts The following salts can be mixed with the uracils of this invention in the listed respective proportions:

Calcium propylarsonate Disodium monomethylarsonate Octyl-dodecylammoniummethylarsonate Dimethyl arsinic acid Mixed in a 1:4 to 8:1 ratio, preferably a 1:2 to 4:1 ratio.

Sodium arsenite Mixed in a 1:10 to 40:1 ratio, preferably a 1:5 to :1 ratio.

Lead arsenate Calcium arsenate Mixed in a 150:1 to 600:1 ratio, preferably a 100:1

to 400:1 ratio.

Sodium tetraborate hydrated, granulated Sodium metaborate Sodium pentaborate Unrefined borate ore such as borascu Polychlorborate Mixed in a 6:1 to 1500:1 ratio, preferably a 3:1 to 1000:1 ratio.

Sodium chlorate Mixed in a 2:1 to :1 ratio, preferably a 1:1 to 20:1 ratio.

Ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to :1 ratio.

Ammonium thiocyanate Mixed in a 1:10 to 20:1 ratio, preferably a 1:5 to 5:1 ratio.

Other organic herbicides The following herbicides can be mixed with the uracils of this invention in the listed respective proportions.

5,6-dihydro-(4A,6A)-dipyrido-(1,2-A,2,l-C)pyrazinium dibnomide Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 ratio.

3-amino-l,2,4-triazole Mixed in a 1:20 to 20:1 ratio, preferably a 1:5 to 5:1 ratio.

3,6-endoxohexahydrophthalic acid Mixed in a 1:4 to 20:1 ratio, preferably a 1:2 to 10:1 ratio.

Diphenylacetonitrile N,N-dimethyl-a,a-diphenylacetamide N,N-di (n-propyl) -2,6-dinitro-4-trifluoromethylaniline N,N-di (n-propyl)-2,6-dinitro-4-methylaniline Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20:1 ratio.

O-(2,4-dichlorophenyl)-o-methyl-isopropylphosphoramidothioate 2,3,5,6-tetrachloroterephthalic acid, dimethyl ester Mixed in a 1:4 to 20:1 ratio, preferably a 1:3 to 15:1 ratio.

2,4-dichloro-4'-nitrodiphenyl ether Mixed in a 1:10 to 30:1 ratio, preferably a 1:5 to 20:1 ratio.

Other substituted uracils The uracils used according to this invention can be mixed with other substituted uracils, in the respective proportions listed below. Methods for the preparation of the listed uracils can be found in copending applications Serial Nos. 159,746, filed December 15, 1961; 89,674, filed February 16, 1961; 167,434, filed February 1, 1962; and 89,672, filed February 16, 1961.

3-isopropyl-5-bromo-6-methyluracil 3-isopropyl-5-chloro-6-met'hyluracil 3-sec.-butyl-5-bromo-6-1nethyluracil 3-sec.-butyl-5-chloro-6-methyluracil 3-cyclol1exyl-5-bromo-6-methyluracil 3-cyclohexyl-5-chloro-6-methyluracil 3-tert.-butyl-5-bromo-6-methyluracil 3-tert.-butyl-5-chloro-6-methyluracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio.

3-cyclohexyl-6-methyluracil 3-cyclohexyl-6-ethyluracil 3-cyclohexyl-6-sec.-butyluracil 3-norbornyl-6-methyluracil 3-cyclopentyl-6 -methyluracil 3-cyclohexyl-6-isopropy1uracil Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1

ratio.

3-isopropyl-1-trichloromethylthio-5-bromo-6-methyluracil 3-cyclohexyl-1-trichloromethylthio-5-bromo-6-methyluracil 3-sec.butyl-1-acetyl-S-bromo-6-methyluracil 3-isopropyl-1-acetyl-5-bromo-6-methyluracil 3-isopropyl-1-trichloromethylthio-S-chloro-6-rnethyluracil Seventeen parts by weight of bromine are added over of the listed S-substituted uracil starting reactants for the 3 -butyluracil:

a 20-minute period to a stirred solution of 19.4 parts by weight of 3-cyclohexyluracil in 100 parts by weight of Uracil starting reactant fi-nitrouracil product glacial acetic acid. The temperature is maintained below 30 C. during the addition. The solution is stirred 3-cyelohcxyluraeil 3-cyclohexyl-5-nitrourncil, at 20-30 C. for an additional 1 /2 hours and is then g' l l" -scc.-amylurac1l 3-sce.-arnyl-5-nitrouracll. [JOllffil mm 2 volumes Of 1C6 water With Stll'l'lllg, where- 3-(3-nitrol-chlorophcnyl) uraciL-.. 3 (3-nitro4-chloropl1cnyl)-5- nitrouraeil. p a f' sohd ?P Thls 5O1 1d 15 filtered! 3. 1 1 1 3 11 1 5 1 washed with water until acid-free, and dried to give es- B-seo-DutyluraeiL 3-scc-.butyl-5-nitrouracil. h 3-cyclooctyluracil. 3-CyCl0OClZyl-54lltIOlll'fiCll. senually Pure 3 cyclo exyl 5 bromouracll 3-cyclobutyluraorL. 3-cyclobutyl-o-nitrouracil.

The following compounds are prepared as in Example B-cyclopentenyluracrl 3-cyclopcutcnyl-anitrouracil. 2 by substituting equivalent amounts of the 3-substituted 3fenchylmclL: 3mnchyl'5rmtr9uraml- 3-norbornyluracil 3-norbornyl-5-n1trourac1l. uracils and halogens set forth in the followmg table for 15 the 3-cyclohexyluracil and bromine:

Uracil starting reactant Parts by Halogen Parts by Uracil product weight weight 3-m-chlorophenyluracil 3-cyclohexyluracil 3-(3-hydroxypropyl) uracil. 3-cyclopentyluracil 3-cycloocty 3-(2-hydroxyethyl)uraeil 3-cyclopentenyluracil.

licp

3-( -1,2,3,4'tetrahydronaphthyl) uracil 3-(1,2,3,4,4a,5,6,7,8,8a-deeal1ydronaphth-6-yl)uracil NRO N 9? r f 1 3- (4-bromocyclohexyl) uracil 3-(5,6,7,8-tetrahydronaphthyl)uracil 3-(m-clilorophcnyl)-5ehlorouracil. 3-cyelohcxyl-S-bromouracil. 3-(ii-hydroxypropyl)-5-chl0rouracil. 3-cyclopentyl-o-bromouracil. 3-cyclooctyl-5-chlorouracil. 3-(2-hydroxycthy])-5-br0rn0uracil. 3-cyclopentcntyl-5-clilorouraeil. 3-(B-cthoxypropyl)-5-l)romouracil. 3-(p-bromophcnyl)-5-chlorouracil. 3-isopropyl-5-br0mouracil. 3-hcxyl-5-chlorouracil. 3-phenyl-5-brornouracil. 3-(3,4-dichlorophcnyl)-5-bromouracil. 3-tcrt.-butyl-5-brornouracil. 3-cyano-5-bromouracil. B-dimcthylamino5-bromouracil. 3mcthoxy-fi-bromourcil. 3-ctl1yl-5-chlorouracil. 3-(B-mcthoxypropyl)-5-bromouracil. 3-scc.amyl-fi-brornouracil. 3-allyl-5-chlorouracil. B- -naphthyl-5-bromouracil. 3-decyl-5-bromouracil. 3-(2-chloroethyl)-5-chl0rouracil. 3-(Q-decenyl)-5-bromouracil. 3-(9,10-dibromodccyl)-5-brom0uracil. 3-(3,4,fi-trichlorophenyl)5'chlorouracil. 3-(bicyclo[2,2,2]oct-5-en-2-yl)-5-bromouracil. 3-(1,2-dimcthyleyclopcntyl)uracil. 3-fenchyl-5-chlorouracil. 3-(chloronorbornyl)-5'br0mouraci1. 3-norbornenyl-fi-bromouracil. 3-(ti-methoxy-3,3-dimcthylindanyl)-5-chl0rouracil. 3-(1,4,5,6-tetrachloro-7,7-dimctl1oxyblcyclo[2,2,1]hept-5- cn-2-ylrnethyl)-5-chlorouracil. 3-(5,G,7,8,10,IO-hexaohloro-l,2,3,4,4a,5,8,8a-octahydro-1,

45.8-dimethano-2-naphthyl)-5-ehlor0uraeil. 3-(3,4-dirnethycyclohcxyl)-5-chl0rouracil. 3-(3a,4,5,6,7,7a-hcxahydro4,7-mcthano-5-indanyl-5-bromouracil., 3-('y-l,2,3,-tetrahydronaphthyl)-5-chlorouracil. 3-(1 i2,3,4,4a,5,6,7,8,Ba-dccahydronaphthyl)-5-brom0ura- 3-(4-bromocyclohexyl)-5-bromouracil. 3-(5,6,7.8-tetrahydronaphthyl)-5-bromouracil.

EXAMPLE 3.-PREPARATION OF 3-BUTYL- 5-NITROURACIL A solution of 40 parts by volume of fuming nitric acid and 40 parts by volume of fuming sulfuric acid S0 is stirred at -30 C. while 18.4 parts by weight of 3 butyluracil are added portionwise over a SO-minu-te period. The entire reaction mixture is stirred an additional minutes, then poured slowly into 4 volumes of stirred ice water. The desired product separates out as a pale yellow solid. It is collected by filtration, washed well with water, and air-dried.

The following S-nitro substituted uracils can be prepared as in Example 3 by substituting equivalent amounts EXAMPLE 4.PREPARATION OF 3-CYCLOHEXYL-5- THIOCYANO-Z-THIOURACIL A vigorously stirred suspension of 39 parts by weight of lead thiocyanate in 200 parts by volume of carbon tetrachloride is slowly diluted with 17.6 parts by weight of bromine. Occasional external cooling is required to hold the temperature of the reaction mixture at 15-20 C. At the end of the addition, stirring is continued until the bromine color is discharged, after which the solution is filtered rapidly under anhydrous conditions. To this solution is added 19.4 parts by weight of 3-cyclohexyluracil, and the resulting mixture is stirred at room temperature for 5 hours. At the end of this time the 17 solvent is removed, leaving essentially pure 3-cyclohexyl- S-thiocyanouracil as a solid residue.

The following compounds can be prepared as in Example 4 by substituting equivalent amounts of the appropriate uracil starting reactants for the 3-cyclohexyluracil:

3-isopropyl-5-thiocyanouracil 3- 1 O-methoxycarbonyldecyl -5-thiocyanouracil 3-allyl-5-thiocyanouracil 3-(ethoxycarbonylmethyl)-5-thiocyanouracil S-(m-pyridyl)-5-thiocyanouracil 3-sec.-butyl-5-thiocyanouracil 3-(1,1,5,S-tetramethyl-S-hydroxypentyl)-5-thiocyanouracil 3-(m-nitrophenyl)-5-thiocyanouracil 3-cyclopropyl-5-thiocyanouracil 3-cyano-5-thiocyanouracil 3-bornyl-5-thiocyanouracil 3-(Z-indanyl)-5-thiocyanouracil 3-cyclohexyl-S-thiocyano-Z-thiouracil EXAMPLE 5.-PREPARATION 0F 3-TERT.-BUTYL- E-THIOCYANOURACIL A mixture of 182 parts of 3-tert.-butyluracil, 700 parts of acetic acid and 152 parts of ammonium thiocyanate is stirred at -15 C. as 160 parts of bromine, dissolved in 180 parts of acetic acid, are gradually added over a period of 2 to 4 hours. When the addition is complete, the mixture is stirred for a short time at C. to insure completion, and then diluted with 9000 parts of ice and Water.

The mixture is then extracted with 4000 parts of dichloromethane. The organic layer is separated, filtered free of polymeric material, washed with sodium bicarbonate solution, dried over magnesium sulfate, filtered, and concentrated to dryness at reduced pressure.

The resulting 3-tert.-butyl-5-thiocyanatouracil can be recrystallized from such solvents as nitromethane or 1, 1,2-trichloroethane.

EXAMPLE 6.PREPARATION OF 3-SEC.-BUTYL- 5 CYANOURACIL A mixture of 116 parts of sec.-butylurea, 66 parts of malononitrile and 444 parts of triethyl orthoformate is heated at 70-100 C. for 3 hours with stirring. The volatile constituents are distilled off at reduced pressure at steam-bath temperature. The resulting solid, [(3-sec.- butylureido)methylene]malononitrile is purified by recrystallizing from a mixture of alcohol and water.

One hundred and ninety-two parts of [(3-sec.-butylureido)methylene]malononitrile, 54 parts of sodium methoxide and 1000 parts of methanol are stirred, protected from atmospheric moisture, and allowed to stand for 5 days at room temperature. The alcohol is removed by distillation at reduced pressure, and the resulting solid is dissolved in 2000 parts of cold water. The solution is made slightly acidic by the gradual addition of acetic acid, and the 3-sec.-butyl-5-cyanocytosine which separates is filtered off, Washed with 1000 parts of cold water and dried.

A solution of 192 parts of 3-sec.-butyl-5-cyanocytosine in 1000 parts of 3 N hydrochloric acid is refluxed for 3 hours and then cooled. The 3-sec.-butyl-5-cyanouracil which separates is filtered off and recrystallized from a mixture of alcohol and Water.

The 5-cyano substituted uracils listed in the following table can be prepared in a similar fashion by substituting equivalent amounts of suitably substituted ureas for 3- sec.-butylurea:

3-isopropyl-5-cyanouracil 3-tert.-butyl-5-cyanouracil 3-(3a,4,5,6,7,7a-hexahydro-4,7-methano-S-indanyl -5- cyanouracil 3-norbornenylmethyl-S-cyanouracil 3-fenchyl-5-cyanouracil EXAMPLE 7.PREPARATION on s-oycLorrnxvn 5-IODOURACIL A mixture of 194 parts of 3-cyclohexyluracil, 1000 parts of acetic acid, and 253 parts of iodine is stirred at C. as 72 parts of fuming nitric acid are gradually added. When the addition is complete, the dark colored solution is refluxed for about one-half hour and then cooled to ice-bath temperature.

The excess iodine which precipitates is filtered off and the filtrate is diluted with 4000 parts by weight of cold water. The iodine remaining in solution is reduced to iodide ion by adding a saturated solution of sodiu bisulfite until the solution becomes colorless.

The aqueous solution is extracted with 6000 parts by Weight of methylene chloride, the organic layer is separated, Washed with saturated sodium bicarbonate solution and distilled under reduced pressure to give solvent-free, essentially pure 3-cyclohexyl-S-iodouracil.

The uracils in the following table can be similarly prepared by substituting equivalent amounts of properly 3- substituted uracils for 3-cyclohexyluracil:

3 -bornyl-5-iodouracil 3-cyclopropyl-5-iodouracil 3-cyclobutyl-5-iodouracil 3-cyclopentyl-5-iodouracil 3-sec.-butyl-5-iodouracil 3-isopropyl-5-iodouracil 3-ethyl-5-iodouracil 3-norbornyl-5 iodouracil 3-dec-ahydronaphthyl-S-iodouracil EXAMPLE 8.PREPARATION OF 3-CYCLOHEXYL 5-HYDROXYMETHYLURACIL A mixture of 19.4 parts by Weight of 3-cyclohexyluracil, parts by weight of Water, 31.5 parts by weight of ethyl alcohol, 6.6 parts by weight of paraformaldehyde, and 2.0 parts by weight of barium hydroxide is heated until all the components are in solution. The mixture is then cooled and the oil which precipitates is extracted with ethyl ether. The ether extract is dried over magnesium sulfate, filtered, and concentrated at reduced pressure to a slightly gummy solid. This solid is recrystallized from acetonitrile to give 3-cyclohexyl-S-hydr-oxymethyluracil.

The following compounds are prepared as in Example 8 by substituting equivalent amounts of other suitable uracil reactants for cyclohexylurea:

3-( m-flu orophenyl -5-hydroxymethy1uracil 3 -ter-t.o ctyl-S -hydroxymethyluracil 3 -.p henyl-S -hydroxymethyluracil 3 5 -cyanopentyl -5-hydroxymethyluracil 3 cyclopentyl-5-hydroxymethyluracil 3- 2-cyanoethyl -5 -hydroxymethyluracil 3- 2-buten-3-y-l -5-hydr-oxyrnethyluracil 3-(5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,6,7,8,8a-decahyd-ro- 5 ,8-methanonaphth-2-ylmetl1yl -5-hydroxyuracil 3 -norbornyl-5 -hydroxymethylur acil 3-o-methylcyclohexyl-5-hydroxymethyluracil 3- 3 a,4,5,6,7,7a-hexahydro-4,7-methano-5indenyl -5- hydroxymethyluracil 3 3 a,4,5 ,6,7,7a-hexahydro-4,7-methano-5-indanyl -5- hyd roxymethyluracil 3- 2,3-dichloro-3 21,4,5 ,6,7,7a-hexahydro4,7-methano-5- indanyl -5-hydroxymethyluracil 3- ('y-decahydronaphthyl -5 -hydroxymethyluracil 3('y-1,2,3 ,4 tetrai1ydronaph-thyl -5-hydroxymethyluracil 3 6-meithoxy-3,3-di-methylindanyl) -5-l1ydroxymethyluracr 3- 5,6,7, 8, 1 0, 1 O-hexachloro- 1 ,2,3 ,4,4a,5,8,8 a-octahydro- 1 ,4,5 ,8-dime-thano-2-naphthyl -5 -hydroxymethy1uracil 3- 3-propyl-2-norcamphanyl -5-hydroxymethyluracil 3 (4-methoxy-3-cyclohexen- 1 -ylmethyl -5-hydroxymethyluracil 3 -fenchyl-5-hydroxymethyluracil 3-b ornyl-5 hydroxymethyluracil 3-(4-bromocyclohexyl -5-hydroxymethyluracil 19 EXAMPLE 9.PREPARATION F 3ISOPROPYL- 5 CHLOROMETHYLURACIL A combination of 15.4 parts by weight of 3-isopropyluracil and 38 parts by weight of chloromethylmethyl other is heated in an autoclave under endogenous pressure at 100 C. for 25 hours. The material is cooled and the excess reagent evaporated under vacuum. The product is extracted from the residue with dry dioxane. The dioxane is then evaporated to dryness, leaving essentially pure 5-chloromethyl-3-isopropyluracil as a residue.

EXAMPLE 10.PREPARATION 0E 5-CHLORO- METHYL-S-NORBORNYLURACIL To 452 parts of rapidly stirred thionyl chloride, maintained at 20-25 C. with an ice bath, are gradually added 206 parts of 5-hydroxymethyl-3-norborny-1uracil. Caution is used in carrying out this reaction because of the large amounts of acidic gases produced and the vigor of the reaction.

A condenser is used to retain the thionyl chloride reactant, and a scrubber washes away the gases evolved in the reaction.

When the uracil is dissolved, the solution is distilled to dryness at reduced pressure at 50 C. The solid is triturated with 200 parts of a 1:1 mixture of 1,1,2-trichloroethane and heptane, and filtered.

The resulting solid 5-chl-oromethyl-3-norbor11yluracil can be recrystallized from nitromethane or 1,1,2-trichloroethane.

The following 5-halomethy-luracils can be prepared by the methods of Examples 9 or 10 by substituting an appropriate uracil for the 3-isopropyluracil of Example 9, or by substituting an appropriate thionyl halide for the thionyl chloride of Example 10.

3-(2-bromoethyl -5-chloromethyluracil 3- 2,4,5 -trichloro phenyl -5 -ch.loromethyluracil 3 (-p-meth oxybenzyl -5-chloromethyluracil 3 3chloro-4-isopropylphenyl -5'chloromethyluracil 3-butynyl-5-chloromethyluracil 3- (dimet-hylaminopropyl -5-chloromethylura cil 3-cyclohexyl-5-bromomethyluracil 3-sec.-butyl-5-bromomethyluracil 3-sec.-butyl-5-fluoromethyluracil 3 -cyclohexyl-5-fiuoromethyluracil EXAMPLE l1.PREPARATION OF 3-CYCLOHEXYL- 5-METHOXYMETHYLURACIL Five hundred parts of methanol, ten parts of chloroacetic acid, and 225 parts of 3-cyclohexyl-5-hydroxymethyluracil are charged into a bomb and heated at 125 C. for 5 hours. The reaction mixture is then concentrated to an oil, which is taken up in 400 parts of acetonitrile, refluxed for a short time with 5 parts of decolorizing carbon, filtered hot and distilled under reduced pressure to yield solvent-free 3-cyclohexyl-5-methoxymethyluracil. The uracils in the following list can be prepared in a similar fashion by substituting equivalent amounts of appropriately substituted uracils and alcohols for 3-cyclohexyl-5-hydroxymethyluracil and methanol:

3-norbornenyl-S-methoxymethyluracil 3-cyclohexyl-5-butoxymethyluracil 3-norbornenylmethyl-5-ethoxymethyluracil 3-norbornyl-S-propoxymethyluracil 3-bornyl-5-methoxymethyluracil 3(3a,4,5,6,7,7a-hexahydro-4,7-methano-S-indenyl)-5- methoxymethyluracil 3-(3a,4,5,6,7,7a-hexahydro-4,7-methano-5-indanyl)-5- methoxymethyluracil 3-decahydronaphthyl-S-methoxymethyluracil 3-(tert.-octyl)-5-methoxymethyluracil EXAMPLE 12.-PREPARATION OF 3-(3-METHYLCYCLO- HEXYL) -5-METHYLTHIOMETHYLURACIL An autoclave is charged with 238 parts of S-hydroxymethyl-3-(S-methylcyclohexyl)uracil, 1500 parts of methanol and 50 parts of methyl mercaptan. The mixture is shaken and heated at 125 C. for 5 hours. It is then cooled and poured into 7000 parts of ice and water.

The white solid Which precipitates is filtered off and recrystallized from acetonitrile or nitromethane, giving pure 3-(3-methylcyclohexyl)-5-methylthiomethyluracil.

The compounds in the following table are similarly prepared by substituting equivalent amounts of the appropriate substituted uracils and equivalent amounts of methyl mercaptan, thiophenol, thioacetic acid or hydrogen sulfide for the 5-hydroxymethyl-3-(3-methylcyclohexyl)uraoil and methyl mercaptan:

EXAMPLE 13.PREPARATION OF 3-BUTYL5- CHLOROURACIL, SODIUM SALT A solution of 4 parts by weight of sodium hydroxide in parts of water is treated with 20.3 parts by Weight of 3-butyl-5-chlorouracil. Stirring and warming is employed to eifect solution. Water is removed under reduced pressure, leaving 3-butyl-5-chlorouracil, sodium salt as a white residue.

EXAMPLE 14.PREPARATION OF TETRABUTYLAM- MONIUM SALT 0F 3-n-BUTYL-zi-METHYLURACIL One hundred eighty-two parts of 3-n-butyl-5-methyluracil are gradually added, with stirring, to 835 parts of a one-molar solution of tetrabutylammonium hydroxide in methanol. When solution is complete, the solvent is distilled off at reduced pressure. The White solid tetrabutylammonium salt of 3-n-butyl-5-methyluracil which remains is sufiiciently pure for incorporation into herbicidal formulations.

EXAMPLE 15.PREPARATION OF A 1: 1 COMPLEX OF 5-BROMO 3 INDANYLURACIL AND PD T -I PHENOL N ACI LORO A dry mixture of 307 parts of 5-bromo-3-indanyluracil and 266 parts of pentachlorophenol is gradually heated until a clear melt results. It is stirred for a short time to insure complex formation, and then cooled. The resulting solid cake can be recrystallized from nitromethane.

EXAMPLE 16.PREPARATION OF THE 2:1 COMPLEX ICZEFi-SNIIIEOMO-3-SEC.-BUTYLURACIL AND p-MEL HOXY- A mixture of 247 parts of 5-bromo-3-sec.-butyluracil, 62 parts of p-methoxyphenol and 600 parts of nitromethane is stirred and heated until the components are dissolved. Ten parts of decolorizing charcoal are added, and the mixture is stirred for a short time and then filtered.

The filtrate is chilled to ice-bath temperature, and the pure, solid 2:1 complex of 5-bromo-3-sec.-butyluracil and p-methoxyphenol is filtered off and dried.

EXAMPLE '17.PREPARATION OF THE ETHYLENEDI- AMINE ADDITION COMPOUND OF BROMO-3ISO- PROPYLURACIL A mixture of 233 parts of 5-bromo-3-isopropyluracil in suificient acetonitrile to form a concentrated solution at room temperature is stirred as 60 parts of ethylenediamine are gradually added.

The solid pure addition compound of 5-bromo-3-isopropyluracil and ethylenediamine which precipitates is filtered oft.

EXAMPLE 18.PREPARATION OF THE ETHANOL AMINE ADDITION COMPOUND OF 3-CYCLOHEXYL S-METHYLURACIL A mixture of 208 parts of 3-cyclo'hexyl-S-methyluracil and 61 parts of ethanolamine is gradually heated. The

resulting liquid is stirred to assure even distribution of the two components, and is then allowed to cool and solidify The resulting solid addition compound is sufiiciently pure for incorporation into herbicidal formulations. If desired, it may be purified by recrystallization from such solvents as acetonitrile or nitromethane.

HERBICIDAL COMPOSITIONS Liquid formulations EXAMPLE 19.AQUEOUS SOLUTION Percent 3-tert.-butyl-5-chlorouracil, Na salt 20 Sodium lauryl sulfate 2 Water 78 These components are prepared as a concentrated aqueous solution by dissolving the two soluble salts in the water, with agitation.

Other soluble salts suitable for preparation of water concentrates are 3-(decahydro-l,4-5,8-dimethanonaphthyl)-5-Inethyluracil, Na salt 3-phenyl-5-thiocyano-2-thiouracil, Li salt 3-butyl-5-cyanouracil, Na salt 3-cyclohexyluracil, Na salt S-fenchyluracil, Na salt 3-( l-ethylhexyl)-5-methyluracil, K salt 3-( l,l-dimethylbutyl)-5-methyluracil, K salt The aqueous solution of 3-(tert.-butyl)-5chlorouracil, sodium salt, is used for directed post-emergence weed control in gladiolus beds. A concentration of one pound of active ingredient per acre in 30 gallons of water gives excellent control of seedling weeds such as crab grass, pigweed, violet Weed, and flower-of-an-hour. Care must be taken to direct the spray so as to avoid contact with the gladiola plants.

At concentrations of to 25 pounds per acre in 80 gallons of water, all of the above compositions give excellent control of a wide variety of annual grasses and broadleaf weeds growing on railroad ballast.

EXAMPLE 20.SOLUTION Percent 3-butyl-5-methyluracil, 2:1 complex with phenol Isophorone 54 Alkylated naphthalene 20 Blend of polyoxyethylene ethers and oil soluble sulfonates 6 These ingredients are mixed with 80 gallons of water and applied at a rate of 1015 pounds of the active compound (2:1 complex) per acre. Excellent kill of weeds, followed by good residual weed control, is obtained on a mixed population of weeds containing quack grass, barnyard grass, crabgrass, seedling Johnson grass, volunteer wheat, pigweed, velvetleaf, and lambs quarters.

EXAMPLE 21.-WATER SUSPENSION A water suspension is prepared by grinding the following ingredients together in a ball or roller mill until 232 the solids are finely dispersed in the water and the average particle size is less than 5 microns:

Percent 3-fenchyl-5-methyluracil 25 Hydrated attapulgite 2 Lignin sulfonic acids, Na sodium salt 5 Water 68 EXAMPLE 22.WATER SUSPENSION A water suspension is prepared by grinding the following ingredients together in a ball or roller mill:

Percent 3-isopropyl-5-bromouracil 25 Hydrated attapulgite 2 Lignin sulfonic acid, Na salt 5 Water 68 Grind-ing is continued until the particles in the suspension have been reduced to diameters of less than 5 microns.

The water suspensions of Examples 23 and 24 control seedling brush growing along fence rows. An application of the suspensions with a pressure sprayer at con centrations of 10 to 20 pounds of active ingredient per acre in 120 gallons of water controls oak and willow seedlings.

EXAMPLE 23.OIL SUSPENSION An oil suspension is prepared by grinding the following ingredients together in a 'ball or roller mill until the sol-ids are finely dispersed in the oil and the average particle size is less than 5 microns:

Percent 3-benzyl-5-chlorouracil 25 Soya lecithin 5 Aliphatic hydrocarbon oil 70 Percent 3-(p-cumyl)-5-thiocyanouracil 25 Diesel oil 67 Polyoxyethylene sorbitan ester of mixed rosin and fatty acids 8 This oil suspension is diluted with water to form a water emulsion and is applied, at a concentration of 24 pounds of active ingredient per acre, as a directed spray to grasses growing in sugar cane. This treatment gives excellent control of mixed annual grasses and broadleaves.

EXAMPLE 25.OIL SUSPENSION The following ingredients are used to prepare an oil suspension:

Percent 3-(p-tolyl)-5-'methyluracil 15 Diesel oil Polyoxyethylene sorbitan esters of mixed rosin and fatty acids 5 The ingredients are ground together in a ball or roller mill until the solids are finely dispersed in the oil and the average particle size of the active ingredient is less than 5 microns. This oil suspension is diluted with water to form a water emulsion for application to plants.

3 (4 isopropylcyclohexylmethyl)-5-brornouracil, 3- (a,oc,oc trifluor-o rn-tolyl)-5-methyluracil, 3-(4-methylcy- 23 cylohexylmethyl --methylu racil, 3 -cyclohexyl-5-bromouracil and 3-cyclopentenyl-S-bromouracil are prepared as oil suspensions in a similar manner.

The emulsifiable oils of Examples 25, 26 and 27 are useful for weed control in railroad yards and cattle yards. When any of these compositions are diluted with water at a rate of 160 gallons per acre and sprayed from a railroad spray car at a level of about 25 pounds of active material per acre, vegetation such as quack grass, crabgrass, seedling Johnson grass, seedling Bermuda grass, brome grass, ragweed, cockleburr, lambs-quarter, and mares-tail is controlled for an extended period.

These same oil suspension compositions, when applied to a drainage ditch infested with mixed annual and perennial broadleaf and grass weeds at concentrations of 25 pounds of active material per acre in 150 gallons of water, also give excellent control of vegetation. The ditch remains bare for an extended period.

EXAMPLE 26.SOLUTION A mixture of 40 parts of 5-bromo-3-isopropyluracil and 60 parts of ethanolamine is stirred at room temperature until a clear solution is formed.

An application of 20 pounds of this formulation per acre (active) in 60 gallons of water per acre controls young and growing cheat grass, foxtail, wild barley, barnyard grass, wild rye, crabgrass, velvet leaf and lambs quarters growing in an outdoor storage yard.

EXAMPLE 27.CONCENTRATE One part of 3-butyl-5-methyluracil, one part of dodecylamine and two parts of aromatic heavy naphtha are blended to give a clear solution.

This formulation, when applied at 20 pounds (active) per acre in 80 gallons per acre of Lion Herbicidal Oil No. 6, gives excellent control of quack grass, seedling Johnson grass, brome grass and sheep sorrel growing on a railroad siding.

EXAMPLE 28.OIL SOLUTIONS Percent 3-isopropyl-5-'bromouracil 10.0 2,3,6-trichlorobenzoic acid 10.0 Xylene 80.0

The solid ingredients are added to the xylene and stirred at ambient temperature until they dissolve.

This solution controls deep-rooted perennial herbaceous weeds and woody vines. A solution of thirty pounds of active ingredients is diluted to 100 gallons with a herbicidal oil and sprayed on a dense tangled growth of vines and weeds along a railroad right-of-way. Good control of trumpet vine, bindweed, poison ivy, barynard grass, foxtail, ragweed, and mares-tail is obtained.

EXAMPLE 29.OIL DISPERSION Percent 3-cyclohexyl-S-methyluracil 25.00 2,4,5-trichlorophenoxyacetic acid, isooctyl ester 6.25 Paratfin oil (90% unsulfonatable residue) 68.75

The uracil and oil are mixed together and wet-milled until the particles are under microns in diameter. The ester is then added to this suspension.

This formulation is extended with No. 2 fuel oil and sprayed at pounds of active ingredients in 50 gallons of oil per acre around electric power poles and transformer stations. Good control of brambles, honeysuckle, goldenrod, poison ivy, pokeweed, corn cockle, panic grass, ragweed, and sow-thistle is obtained.

EXAMPLE 30.EMULSIFIABLE CONCENTRATE Percent 3-butyl-5-methyluracil 20 Alkyl, aryl polyether alcohol 5 Dibutyl ketone 75 A concentrate is prepared by mixing the three components. It can be extended with water to give an emulsion.

This formulation is extended with 30 gallons of water and used in post-emergence applications at levels of 1 to 2 pounds of active ingredient per acre on young germinating annual weeds in established asparagus beds. It is applied in the spring, prior to the emergence of the asparagus spears. Good control of foxtail, lambs quarters, pigweed and cocklebur is obtained.

Solid formulations EXAMPLE 31.SOLUBLE POVDER Percent 3-butyl-5-chlorouracil, sodium salt 90 Diatomaceous silica 10 A noncaking, soluble powder is prepared by blending and micropulverizing these ingredients. When the powder is placed in water in a spray tank, the active material dissolves, leaving the silica in suspension.

This soluble salt composition is used for control of mixed annual and perennial vegetation growing around oil tank installations. Concentrations to 20 to 30 pounds of active ingredient per acre in 80 gallons of water give excellent weed control for an extended period.

Other soluble uracil salts which can be prepared and used in the same manner, with good results are 3-cyclohexyl-5-bromouracil, potassium salt 3-benzyl-5-thiocyano-2-thiouracil, lithium salt 3-allyl-5-propyluracil, sodium salt 3-decyl-5-fiuorouracil, potassium salt EXAMPLE 32.-WATER SOLUBLE IOVDER Percent 3-butyl-5-methyluracil 50.0 Trisodium phosphate (anhydrous) 42.5 Sodium lignin sulfonate 5.0 Sodium lauryl sulfate 2.5

EXAMPLE 33.PELLETS Percent 3-butyl-5-bromouracil 25 Alkyl naphthalene sulfonic acid, Na salt 1 Anhydrous sodium sulfate 10 Non-swelling clay 64 This composition is blended and micropulverized, then mixed with 1520% water and extruded under pressure through an orifice to produce rods which are cut into pellets and dried.

EXAMPLE 34.PELLETS Parts 3-propynyl-5-bromouracil 190 Water 280 Hide glue (20% aqueous) 65 Glass frits (2030 mesh) 750 The active ingredient is first made into an aqueous suspension by ball milling with the water and hide glue. The aqueous suspension is then sprayed onto the glass frits with continuous agitation in a ribbon blender. When complete coverage is obtained, the frits are removed and dried in a tunnel drier.

EXAMPLE 35.PELLETS (FAST RELEASE) Percent 3-allyl-5-fiuorouracil 25 Non-swelling Ca, Mg bentonite 25 This mixture is first blended, then micropulverized. The product is moistened with 20-23% water and extruded through a A; inch orifice. The extrusions are cut into /s inch pellets, which are then dried.

EXAMPLE 36.--PELLETS Pellets with a moderately rapid rate of release are prepared as follows:

. Percent 3-butyl-5-cyanour acil 12 Polyvinyl alcohol (low viscosity) 2 Water 16 Prilled sodium nitrate (2-4 mesh) 70 The active ingredient is first ball milled with the polyvinyl alcohol and water to form a thin paste, which is then added slowly to a ribbon blender agitating the prilled sodium nitrate. Steam heat can be applied to a jacket on the ribbon blender to hasten the drying. Blending and drying are continued until the coating adheres firmly.

3-isopropyl-5-bromouracil can be similarly formulated.

EXAMPLE 37.PELLETS Percent 3-norbornyl-S-methoxymethyluracil 25.0 Anhydrous sodium sulfate 10.0 Alkyl naphthalene sulfonic acid, Na salt 1.0 Non-swelling Ca, Mg bentonite 64.0

These components are prepared as pellets by first blending and grinding them in a micropulverizer, moistening them with 18-22% water and then extruding them through a die having Aa-inch holes. The extrusions are cut at the die face into As-inch lengths and dried.

Other compounds suitable for formulation in a similar manner are Any of the pellet compositions of Examples 33-37 can be applied by hand at a level of 25 pounds of active ingredient per acre for control of annual and perennial weeds along guard rails, safety fences, and highway markers and dividers.

The same compositions, when applied by airplane at concentrations of 12-18 pounds of active material per acre, give effective control of willow and oak.

EXAMPLE 3S.PELLETS Percent 3-(4methoxycyclohexyl)-5-methoxyrnethyluracil 25 Methyl cellulose, low viscosity 3 Kaolin clay 72 These components are blended and micropulverized, then pug-milled with 15% to 20% water, and extruded through Ax-inch die holes. The extrusions are cut into /s-inch segments, then dried.

The following uracils can also be formulated in this way.

3-(4-isopropylcyclohexyl)-5-hydroxymethyluracil 3- (4-methoxycyclohexyl)-5-methyluracil 3-(5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,6,7,8,8a-decahydro-S,S-methanonaphth-Z-ylmethyl) -5-hydroxymethyluracil 3- (4-methoxycyclohexylmethyl -5-methoxyuracil 3- [2- (4-bromocyclohexyl )ethyl] -5-nitrouracil 3- 1 ,2,3 ,4-tetr ahydronaphthyl -5-methyluracil These formulations, applied in 60 gall-ons of water at the rate of 25 pounds (active) per acre, control crab grass, barnyard grass, foxtail, pigweed, and lambs quarters growing along boardwalks.

EXAMPLE 39.GRANULES Percent 3-allyl-5-chlorouracil 20 Attapulgite clay 78 Alkyl naphthalene sulfonic acid, Na salt 1 Lignin sulfonic acid, Na salt 1 The ingredients are mixed in a ribbon blender until they are homogeneous and are then charged to a pug mill, where sufficient water is blended in to form a thick paste. The paste is discharged from the pug mill in the form of extrusions which are dried and broken by means of a rotary crusher into irregular granules roughly inch to 42. inch in diameter.

3-isopropyl-S-nitrouracil is also formulated into herbicidal granules by this method.

EXAMPLE ML-GRANULES The procedure of Example 41 is used with the following ingredients to give herbicidal granules of high density:

Percent 3-butyl-5-ch1orouracil 12 Sand (20-30 mesh) 81 Sodium silicate (28% SiO ratio SiO /Na O=3.25) 7 EXAMPLE 41.GRANULES (FAST RELEASE) Percent 3-(sec.-amyl)-5-methyluracil, sodium salt 20 10-20 mesh granular, expanded vermiculite The active ingredient is dissolved in water and the solution is then sprayed on the vermiculite while it is tumbled in a blender. The product is then dried.

EXAMPLE 42.GRANULES This product is prepared in the same manner as in Example 43, using the following ingredients:

Percent 3-(sec.-butyl)-5-chlorouracil, Na salt 2 Granular 15-30 mesh Attaclay 98 EXAMPLE 43.GRANULES Percent 3-phenyl-5-chlorouracil, sodium salt 25 8-20 mesh expanded vermiculite 75 This composition is prepared by dissolving the active ingredient in water and spraying it on tumbling vermiculate and then drying the product.

Other compounds suitable for the preparation of this type of granule are 3-(p-methoxybenzyl)-5-methyl-2-thiouracil, sodium salt 3-b-enzyl-5-nitrou1'acil, potassium salt 3-cycl0octyl-S-thiocyanouracil, sodium salt 3-propynyl-5cyano-2-thiouracil, sodium salt 3-(3-methoxypropyl)-5-bromouracil, lithium salt 3-('y-decahydronaphthyl)-5-chlorouracil, sodium salt 3-(bornyl)-5-fluorouracil, sodium salt 3-(5,6,7,8,10,lO-hexachlorodecahydro-l,4-5,8-dimethano-2-naphthyl)uracil, sodium salt 3-(3,4-xylyl)-5-methyluracil, potassium salt 3-(p-butylbenzyl)-5-methoxymethyluracil, sodium salt Any of the granular compositions of Examples 39-43 can be applied by hand or by specially built spreaders at concentrations of 25 to 30 pounds of active ingredient per acre, for the control of broadleaf and grass weeds in lumber yards, along railroad rights-of-way, fire lanes and around billboards, and in parking areas and roadsides. They can also be applied as soil treatments, at 20-30 pounds of active material per acre, for control of young woody plants such as oak, maple, and willow.

EXAMPLE 44.--GRANULES Percent 3-norbornyl-5-(methylthiomethyl)uracil 25 Lignin sulfonic acid, sodium salt 1 Alkyl naphthalene sulfonic acid, sodium salt 1 Attapulgite clay '73 After blending, these ingredients are charged to a pug mill and sufiicient water is added to form a thick paste. The paste is extruded through a suitable orifice, broken, and dried.

The following uracils can be similarly formulated:

3- 3 ,4,5-trichlorophenyl) -5-methyluracil 3- (p-fluorophenyl)-5-ethylthiouracil 3- S-nitrofurfuryl -5-butylthiouracil 3- (p-chlorobenzyl) -5-iodouracil 3-( 3,4-dichlorobenzyl)-5-bromomethyluracil 3-[p-(sec.-butoxy) benzyl] -5-bromouracil 3-(3-methyl-4-chlorophenyl)-5-methyluracil 3- (p-nitrobenzyl -5-methoxymethyluracil 3-isopropyl-5-allyluracil 3-isopropyl-S-thiolmethyluracil 3-cyclopentyl-5 -chloromethyluracil 3-isopropyl-5-phenylthiomethyuracil 3 -cyclohexyl-5-carb oxymethylthiomethyluracil 3-(5-nitro-2-furfuryl)-5-butylthiouracil Twenty pounds (active) of these formulations, applied as the weeds emerge, give excellent control of crab grass, foxtail, barnyard grass, lambs quarters, fiower-of-thehour and chickweed growing around guard rails and highway signs.

EXAMPLE 45.GRANULES Percent 3-cyclohexyl-S-bromouracil 2.00 Alkyl napthalene sulfonic acid, Na salt 0.02

Sodium chlorate, 40%-sodium metaborate 60% 97.98

The mixture of sodium chlorate and sodium metaborate is charged to a drum blender. The uracil and surfactant are blended, micropulverized, slurried in water, and then sprayed on the granular mass in the blender.

This formulation controls weeds around sign posts, bridges abutments, trestle supports, signal lights, and hand switches along a railroad. The granules are distributed by hand at about 2 pounds per 100 square feet and give outstanding control of broomsedge, foxtail, ragweed, pig weed, knotweed, morning glory, brambles, and seedling Johnson grass.

EXAMPLE 46.PELLETS Percent 3-(tert.-butyl)-5-bromouracil 10.0 Phenyldimethylurea 10.0 Kaolin clay 77.0 Low viscosity methyl cellulose 3.0

The ingredients are blended, micropulverized, pugmilled with to water, and extruded through /s-inch holes. The extrusions are then cut to fis-inch lengths and dried.

These pellets are scattered along a powerline right-ofway at 200 pounds per acre. Excellent control of small oaks, elms, maples, and poplar encroaching on the rightof-way is obtained.

EXAMPLE 47.-TANK MIX A wettable powder is prepared by blending and micropulverizing the following ingredients:

Percent 3-cyclohexyl-S-bromouracil 80.00 Dioctyl sodium sulfosuccinate, 85-15 condensate with sodium benzoate 1.00

Low viscosity methyl cellulose 0.25

Attapulgite clay 18.75

Twenty-five pounds of this wettable powder and 23.5 pounds of an formulation of 2,2-dichloropropionic acid, sodium salt, are mixed thoroughly in 150 gallons of water. This spray mixture, applied at 150 gallons per acre along a highway shoulder, gives good control of a heavy population of Johnson grass, lambs quarters, ragweed, barnyard grass, smartweed, pigweed, and goatweed. The shoulder remains free of these troublesome weed species for an extended period.

EXAMPLE 4S.TANK MIX Wettable powders are prepared by separately blending and micropulverizing the following groups of ingredients:

Percent 3-cyclohexyl-5-bromouracil 60.00 Alkyl naphthalene sulfonic acid, Na salt 1.50 Partially desulfonated sodium lignin sulfonate 1.00 Kaolin clay 37.50

Percent 3-(sec.-butyl)-5-bromo-6-methyluracil 80.00 Sodium dodecylbenzene sulfonic acid 1.50 Low viscosity methyl cellulose 0.25

Attapulgite clay 18.25

These two wettable powders are mixed in gallons of water. Both powders are added to the water in the amount of 10 pounds of active ingredient.

This spray mixture is applied to a railroad right-of-way at 100 gallons per acre. It gives exceptional control of Johnson grass, Bermuda grass, goldenrod, spotted spurge, smartweed, and ragweed. The area remains free of weeds for an extended time.

EXAMPLE 49.\VETTABLE PO\VDER Percent 3-phenyl-5-bromouracil 80.0 Calcium lignin sulfonate 0.5 Sodium arylalkyl sulfonates 2.0 CaSO -2H O 2.0

3:1 weight ratio of attapulgite clay to tricalcium phosphate 15.5

Applied as a pre-emergence treatment, 3 pounds (active) of this formulation per acre in 60 gallons of water gives excellent control of crab grass, foxtail, carpet weed and pigweed in a newly planted field of peanuts.

EXAMPLE 50.WETTABLE POWDER A wettable powder is prepared by blending the following components in a ribbon blender, micropulverizing in a hammer mill until the particles are below 50 microns in size, and then reblending until homogeneous.

Percent 3-cyclohexyl-S-methyluracil 80.00 Attapulgite clay 17.25 Alkyl napthalene sulfonic acid, Na salt 2.00 Low viscosity methylcellulose 0.25 Dioctyl sodium sulfosuccinate 0.50

Two pounds of this wettable powder composition in 30 gallons of water are applied as directed spray to grasses and broadleaf weeds growing in safflower. Wild mustard, millet, barnyard, and crab grass are killed. Four to eight pounds of active ingredient per acre give excellent control of quack grass growing along fence rows.

At concentrations of 15 to 20 pounds of active ingredient per acre, this composition also gives excellent control of annual and perennial weeds growing on railroad rights-of-way and industrial sites.

3-isopropyl-5-bromouracil and 3-butyl 5 bromouracil are also formulated as wettable powders and used in this manner, with equivalent results.

29 EXAMPLE 51.WETTABLE POWDER Percent 3-butyl-5-chlorouracil, Ca salt 80 Dodecylbenzene sulfonic acid, Na salt 2 Sodium lignin sulfonate l Attapulgite clay 17 These ingredients are prepared as a wettable powder in the same manner as shown in Example 50.

Other insoluble or sparingly soluble uracil salts suitable for such formulation are:

3-cyclohexyl-5-chloro-2-thiouracil, Ca salt 3-butyl-5-bromo-2-thiouracil, Mg salt 3-phenyl-5-ethyluracil, Ca salt 3-fenchyl-S-hydroxymethyluracil, sodium salt 3- (3 -chloro-4-nitrophenyl -5-methyluracil manganous salt 3- 3-chloro-4-methoxyphenyl -5-bromo-2-thiouracil,

iron salt EXAMPLE 52.WETTABLE POWDER Percent 3-cyclohexyl-5-thiocyanouracil 80.0 Dioctyl sodium sulfosuccinate concreted with sodium benzoate 0.4 Ditertiary acetylenic glycol 0.5 Oleylester of sodium isethionate 1.0 Attapulgite clay 18.1

This wettable powder -is also prepared in the manner described in Example 50.

EXAMPLE 53.-ETTABLE POWDER A wettalble powder is prepared by blending the following components in a ribbon blender, followed by micropulverizing in a hammer mill. The ground product is air-reduced until the particles are below microns in size and is then reblended until homogeneous: Percent 3-phenyl-5-chlorouracil 50.00 Synthetic precipitated hydrated silicon dioxide 45.75 Low viscosity methylcellulose 0.2-5 Al kyl naphthalene sulfonic acid, Na salt 2.00 Polyoxyethylene esters of mixed fatty and rosin acids 2.00

EXAMPLE 54.WETTABLE POWDER Percent 3-norbornenylmethyl-5-hydroxymethyluracil 50.0 Alkyl naphthalene sulfonic acid, sodium salt 1.0 Sodium salt of polymerized alkyl naphthalene sulfonic acid 0.5 Calcined, non-swelling Montmorillonoid type clay (Pikes Peak clay) 48.5

This wettable powder is prepared in the same manner as described in Example 53.

Other active materials which make satisfactory wettable powders according to this procedure are 3-naphthylmethyl-5-methoxyrnethyluracil 3 (m-ohlorophenyl -5 -bromouracil 3-allyl-5-thiocyanouracil 3 -benzyl-5-methyl-2-thiouracil 3- (Z-cyanoethyl -5-methoxymethyluracil 3- 3 a,4,5,6,7,7a-hexa hydro-1,4-metl1ano-5-indenyl) 5 chlorouracil 3- 3a,4,5 ,6,7,7ahexahydrb-1,4 methano- 5-indanyl) 5 -hydroxymethyluracil 3- p-an'isyl -5 -c-hlorouracil 3 butyl-5 -methyluracil 3 -phenyl-5-bromouracil 3- (p-methylbenzyl -5 -methyluracil EXAMPLE 55.WETTABLE POWDER A wettable powder is prepared by blending the following components in a ribbon blender, micropulverizing them in a hammer mill until the particles are all 30 below microns in size, and then reblending until the powder is homogeneous:

Percent 3-(fl-pbenethyl)-5-chlorouracil 25 Kaolin clay 70 Dioctyl ester of sodium sulfonsuccinic acid 1 Sodium lignin sulfonate 4 EXAMPLE 56.WETTABLE POWDER A wettable powder is made by blending the following ingredients in a ribbon blender:

Percent 3-butyl-5-chloro-2-thiouracil 50 Diatomite 46 Polymerized sodium salts of alkyl naphthalene sulf-o-nic acid 2 Glyceryl monostearate 2 After blending, the composition is micropulverized in a hammer mill until the particles are all less than 50 microns in size. The product is finally reblended in a ribbon blender until homogeneous.

EXAMPLE 57.WETTABLE POVDER Percent 3-isopropyl-5 fluoro-2-thioura cil Synthetic calcium silicate 38 Polyvinyl alcohol (low viscosity) 1 Alkyl naphthalene sulfonic acid, Na salt 1 The components are blended in a ribbon blender, m-icropulverized in a hammer mill until the particles are below 50 microns in diameter, and then reblended in a ribbon blender unt-il homogeneous.

EXAMPLE 58.WETTABLE POWDER A Wetta'ble powder is prepared by blending the following ingredients in a ribbon blender:

Percent 3-cyclooctyl-5-nitrouracil 60.00 Attapulgite clay 38.90

Dioctyl ester of sodium sul fosuccinic acid 0.40 Low viscosity methylcellulose 0.30 Aliphatic substituted butynediols and octynediols 0.40

The blended mixture is ground in a hammer mill until the particles have a diameter of less than 50 microns. The ground product is then reblended until homogeneous.

EXAMPLE 59.-WETTABLE POWDER A wettable powder formulation is prepared by blending the following components in a ribbon blender:

Percent 3-cycloheptyl-S-propyluracil 50 Kaloin olay 46 Diotcyl ester of sodium sulfosuccinic acid 1 Sodium lignin sulfonate 3 EXAMPLE GO.VVETTABLE POWDER Percent 3-isopropyl-5-methyluracil, 1-1 addition compound with octyl amine 40.0 Alkyl naphthalene sulfonic acid, sodium salt 1.0 Low viscosity methyl cellulose 0.3

Attapulgite clay 58.7

These components are blended, micropulverized, and reblended to give a homogeneous powder.

This wettable powder is applied as a pre-emergence treatment, at a rate of pounds of active herbicide per acre in gallons of water, to the area surrounding an outdoor electrical transformer and switching station. When so applied, it gives excellent control of seedling Bermuda grass, seedling bindweed, wild mustard, giant foxtail, crab grass, barnyard grass, and chickweed.

EXAMPLE 61.WETTABLE POWDER A wettable powder is prepared by blending the following ingredients in a ribbon blender:

Percent 3-decyl-5-chlorourasil 70.00 Attapulgite clay 28.25 Alkyl naphthalene sulfonic acid, Na salt 1.50 Low viscosity methylcellulose 0.25

The blended mixture is micropulverized in a hammer mill until the particles are all less than microns in size, and is then remixed in a ribbon blender until homogeneous.

EXAMPLE 62.WETTABLE POWDER Percent 3-(3,4-dichlorophenyl)-5-ch1orouracil 50 Kaolin clay 48 Dioctyl ester of sodium sulfosuccinic acid 1 Sodium lignin sulfonate l The ingredients are mixed together in a ribbon blender and micropulverized in a hammer mill until the particles are below 50 microns in size.

The ground product is then remixed in a ribbon blender until homogeneous.

EXAMPLE 63.\VETTABLE POVDER Percent 3-(sec.-butyl)-5-bromouracil 40.00 2-methylmercapto-4-ethylamino-6-isopropylamino s-triazine 40.00

Alkyl naphthalene sulfonic acid, Na salt 1.75

Low viscosity methyl cellulose 0.25

Attapulgite clay 18.00

These ingredients are formulated into a wettable powder by blending and micropulverizing them until the particles are under 50 microns in size.

This formulation controls pernicious weed populations in oil refineries around oil storage tanks, pipelines, vents, and valves. Thirty pounds of the 80% powder in 100 gallons of Water per acre gives rapid kill of fingergrass, foxtail, lovegrass, crab grass, broomsedge, sand spur, marestail, ragweed, beggarticks, and spurge.

EXAMPLE 64.WETTABLE POWDER Percent 3-norbornyl-5-bromouracil 16.0 Disodium monomethylarsonate 64.0 Alkyl naphthalene sulfonic acid, Na salt 0.5 Sodium lignin sulfonate 1.0

Kaolin clay 16.0 Synthetic fine silica 2.5

These components are blended and micropulverized until the particles are under 50 microns in size.

This composition controls crab grass in arbor vitae when dispersed in 100 gallons of water and sprayed preemergence at 5 pounds per acre when the crab grass starts to emerge. The composition also controls chickweed.

EXAMPLE 65.WETTABLE POWDER Percent 3-cyclohexyl-5-chlorouracil 25.0 3-(3,4-dichlorophenyl)-l-methoxy-l-methylurea 25.0 Kaolin clay 40.0 Synthetic fine silica 3.0 Alkyl naphthalene sulfonic acid, Na sal 2.0 Partially desulfonated sodium lignin sulfonate 5.0

These ingredients are blended, micropulverized, and then passed through an air attrition mill to reduce the particle size to approximately 5 microns or less.

This formulation is sprayed on a sugar cane crop at 1.5 pounds of active ingredients in 60 gallons of water per acre when the cane is about 12 inches tall and the Weeds are less than 4 inches tall. Excellent control of foxtail, water grass, annual morning glory, butter print, pigweed, ragweed, crab grass, and spotted spurge is obtained without perceptible injury to the cane.

EXAMPLE 66.WETTABLE POWDER Percent 3-cyclohexyl-5-bromouracil, 1:1 complex with pentachlorophenol Alkyl naphthalene sulfonic acid, sodium salt 2 Partially desulfonated sodium lignin sulfonate 2 Attapulgite clay 16 These ingredients are blended and micropulverized until the particles wet screen through 325 mesh.

The formulation is applied at the rate of 30 pounds of the active compound (1:1 complex) per acre in 60 gallons of water, to annual and perennial weeds growing around electric towers and highway sign posts. Excellent initial kill of the weeds is obtained. Weed species which are controlled are cheat crab grass, seedling Johnson grass, brome grass, foxtail, ryegrass, quack grass, bluegrass, purslane, Spanish needle, mustard and velvetleaf.

This same spray mixture is also applied to a railroad right-of-way at gallons per acre. It gives exceptional control of seedling Johnson grass, seedling Bermuda grass, goldenrod, spotted spurge, smartweed, and ragweed. The area remains free of weeds for an extended time.

EXAMPLE 67.WETTABLE POWDER Percent 3-sec.-butyl-5-iodouracil 40.00 Dioctyl ester of sodium sulfosuccinic acid 0.40 Low viscosity methyl cellulose 0.30 Aliphatic substituted butyndiols and octyndiols 0.40 Kaolin clay 58.90

These ingredients are blended, ground in a hammer mill until the particle diameters are 50 microns or less, and then reblended.

The following uracils can be similarly formulated:

3- 3-chlorol-meth ylpropyl -5-ethyluracil 3 (4-bromobutyl -5-methy1uracil 3-hydroxyethyl-5 -methy1thioluracil 3-ethoxycarbonylmethyl-S-bromouracil 3-dimethylaminoethyl-5-methoxymethyluracil 3 -methoxyethyl-S-hydroxymethyluracil 3 p-brom ophenyl -5-hydroxymethyluracil 3- 3 ,4-dibromophenyl -5-hydroxyrnethyluracil 3- p-nitrophenyl -5-methyluracil 3 3 ,4-dimethylbenzyl) 5- 2-hyd roxypropyl uracil 3-propynl-5-methyluracil 3 -cyano-5-bromouracil 3-(4-isopropyl-2-methylbenzyl)-5-bromouracil These formulations, applied as foliar sprays at 25 pounds (active) per acre in 60 gallons of water to emerging weeds, give excellent control of crab grass, foxtail, chickweed and volunteer small grains growing around loading platforms.

The embodiments of the invention in which an exclusive property or privilege is claimed are:

1. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected from such vegetation, a herbicidally effective amount of a compound selected from the group consisting of where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms,

substituted of alkyl of 1 through 10 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano,

aryl of 5 through 14 carbon atoms,

substituted aryl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkoxy, alkyl, nitro, trifluoromethyl, 1,2rtetramethylene, and 1,2-trimethyleneylene,

arylalkyl of 5 through 15 carbon atoms,

substituted arylalkyl of 5 through 15 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, alkyl, nitro, and alkoxy,

tetrahydronaphthylalkyl,

alkenyl of 3 through carbon atoms,

alkynyl of 3 through 10 carbon atoms,

cycloalkyl of 3 through 12 carbon atoms,

substituted cycloalkyl of 3 through 12 carbon atoms, wherein substituent selected from the group consisting of bromine, chloride, methoxy, and alkyl,

cycloalkenyl of 4 through 12 carbon atoms,

substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substitutent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

cycloalkyl alkyl of 4 through 13 carbon atoms, cycloalkenyl alkyl of 5 through 13 carbon atoms,

(substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

(substituted cycloalkenyl)alkyl of 5 through 14 cabron atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and

R is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl,

ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro,

alkoxyrnethyl of 2 through 6 carbon atoms,

hydroxy alkyl of 1 through 6 carbon atoms,

alkenyl of 3 through 6 carbon atoms, thiocyano, cyano, methylthiol,

alkylthio of 1 through 4 carbon atoms,

methylthiomethyl, chloromethyl, bromomethyl, fluoromethyl, phenylthiomethyl, and carboxymethylthiomethyl,

with the proviso that R can be hydrogen when R is selected from the group consisting of cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl; and

X is selected from the group consisting of oxygen and sulfur; and (b) the sodium, potassium, lithium, calcium, magnesium, barium, strontium, iron, manganese, and quaternary ammonium salts of the compounds in (a).

2. The method of claim 1 wherein the herbicidal active compound is 5-bromo-3-phenyluracil.

3. The method of claim 1 wherein the herbicidal active compound is 3-butyl-5-methyluracil.

4. The method of claim 1 wherein the herbicidal active compound is 3-cyclohexyl-S-bromouracil.

5. The method of claim 1 wherein the herbicidal active compound is 3-cyclohexyl-S-methyluracil.

6. The method of claim 1 wherein the herbicidal active compound is 3-norbornyl-5-methyluracil.

7. The method of claim 1 wherein the herbicidal active compound is 3-sec.butyl-5-methyluracil.

8. The method of claim 1 wherein the herbicidal active compound is 3-sec.-tbutyl-5-chlorouracil, sodium salt.

9. The method of claim 1 wherein the herbicidal active compound is 3-tert-butyl-5-bromouraci1.

10. The method of claim 1 wherein the herbicidal active compound is 3-tert-butyl-S-chlorouracil, sodium salt. 3-cyclopropylmethyl-S-methyluracil 11. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected from such vegetation, a herbicidall effective amount of a compound selected from the group consisting of:

(a) compounds of the formula where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms,

substituted alkyl of 1 through 10 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano,

aryl of 5 through 14 carbon atoms,

substituted aryl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenyl, alkoxy, alkyl, nitro, trifluoromethyl, 1,2-tetramethylene, and 1,2-trimethylenylene,

arylalkyl of 5 through 15 carbon atoms,

substituted arylalkyl of 5 through 15 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, alkyl, nitro, and alkoxy,

tetrahydronaphthylalkyl,

alkenyl of 3 through 10 carbon atoms,

alkynyl of 3 through 10 carbon atoms,

cycloalkyl of 3 through 12 carbon atoms,

substituted cycloalkyl of 3 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

cycloalkenyl of 4 through 12 carbon atoms,

substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

cycloalkyl alkyl of 4 through 13 carbon atoms,

cycloalkenyl alkyl of 5 through 13 carbon atoms,

(substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substitutent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

(substituted cycloalkenyl)alkyl of 5 through ((1) compounds of the formula 14 carbon atoms, wherein said substituent is selected from the group consisting of bro- H O mine, chlorine, methoxy, and alkyl, and X ll cyano; R1

R is selected from the group consisting of RT I chlorine, fluorine, bromine, iodine, methyl,

ethyl, propyl, butyl, methoxy, ethoxy, pro- Y I \N/ n poxy, butoxy, nitro, alkoxymethyl of 2 through 6 carbon atoms, 10

hydroxy alkyl of 1 through 6 carbon atoms, Where alkenyl of 3 through 6 carbon atoms, R F 1 are as defined above, thiocyaho, cyano, methylthiol X 1s selected from the group cons1st1ng of alkylthio of 1 through 4 carbon atoms, hydrogen chlorlne, 111m), methylthiomethyl, chloromethyl, bromomethalkyl P 1 through 3 carbon atoljns,

Y1, fl th l phenylthiomethyh and bromlne and CR where R 1s alkyl of 1 carboxymethylthiomethyl, through 3 carbonatoms; t with the proviso that R1 can he hydrogen when Y 1s selected from the group cons1st1ng of chlorine R is selected from the group consisting of cyallkyl of 1 through 3 carbon atoms; cloalkyl, cycloalkenyl, cycloalkyl alkyl, and "U a Whole number 1 through f cycloatkehyl alkyh 11 1s selected from the group conslstlng of 1 and 2. and

X is selected from the group consisting of oxygen References Cted by the Exammer and sulfur; UNITED STATES PATENTS (b) the sodium, potassium, lithium, calcium, magnesi- 2,567,651 9/1951 Papesch et a1 um, barium, strontium, 1ron, manganese, and quater- 2,688,020 8/1954 Mackay at at nary ammomum salts of the compounds 1n (a); 2,969,364 1/1961 Lyme X (6) compounds of the 'fmmula 3,002,975 10/1961 Slezak 71-25 X 0 3,086,854 4/1963 Harvey 71-25 3,097,944 7/1963 Riddell et al. 71-2.s m NB OTHER REFERENCES =L Bonner et al., Proc. Natl. Acad. Sci., 25, pp. 184-188 f 1939 H Thompson et al., Botanical Gazette, 107, pp. 475-507 Where 1946) R and R are as defined above, and NB is a nitrogenous base having an ionization con- LEWIS GOTTS Pr'mary Exammer stant K kl0 in Water; and 40 JULIAN S. LEVITT, Examiner. 

11. A METHOD FOR THE CONTROL OF UNDERSIRABLE VEGETATION, SAID METHOD COMPRISING APPLYING TO A LOCUS TO BE PROTECTED FROM SUCH VEGETATION, A HERBICIDALLY EFFECTIVE AMOUNT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (A) COMPOUNDS OF THE FORMULA 